Investigation of the Major Odor Contributors and Health Risk Assessment in the Organophosphorus Pesticide Field
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摘要:
农药污染地块修复过程中频繁出现异味污染问题，严重影响周边居民日常生活和身体健康。以往报道多集中在场地内有毒有害物质分析，较少关注场地异味污染问题。为预测某有机磷农药场地修复过程异味污染情况，本文以该地块7个潜在异味污染控制区为研究对象，分析了近土壤空气异味污染程度和影响范围，并应用气相色谱-四极杆/静电场轨道阱高分辨质谱技术测定近土壤空气、土壤中挥发性有机物（VOCs）和半挥发性有机物（SVOCs），阐明地块控制区内异味污染排放特征，评估近土壤空气地块污染的人体健康风险。结果表明，7个区域监测点位散发不同程度刺激性气味，臭气浓度值范围为309~72443；生产区异味影响范围最大，达到3.2km；共识别出近土壤环境空气中209种VOCs、土壤样品中246种VOCs和SVOCs，主要包括芳香化合物、卤代物、烷烯烃和含氧有机物；主要异味贡献物质种类包括有机硫化物、芳香化合物和含氧有机物；7个区域近土壤空气均存在致癌风险（>1.0×10-4），5个区域存在非致癌风险，主要致癌物质为1，4-二氯苯、苯、四氯化碳。本文开展的农药场地异味物质组分与致病致癌风险持续研究结果，可为研究区生态环境修复和居民健康保护等提供重要依据。
Abstract:BACKGROUND Odorous gases, derived from organic decomposition in the soil, frequently cause odor nuisances, seriously affecting the daily life and health of surrounding residents. In the past, reports mostly focused on the analysis of toxic and hazardous substances in the site, and less attention was paid to the problem of site odor pollution.
OBJECTIVES To predict the odor pollution of an organophosphorus pesticide site during the restoration, clarify the characteristics of odor pollution emission in the control area, and assess the human health risk of the pollution of the air near the soil.
METHODS 7 potential odor pollution control areas were selected as the research objects, and the pollution degree and impact range of the nearby soil air odor was analyzed. Sensory analysis, gas chromatography high-resolution mass spectrometry (GC-HRMS) and reference concentrations (RfC) and inhalation slope factor (SF) were used.
RESULTS The air near the soil in 7 areas showed different degrees of pungent odors with the odor concentration (the dilution multiple required to dilute the odor gas with odorless air to just no odor) ranging from 309 to 72443. The odor in the production area had the largest impact range, reaching 3.2km; a total of 209 volatile organic compounds (VOCs) in the ambient air near the soil, and 246 VOCs and semi-volatile organic compounds (SVOCs) in the soil samples were identified, mainly including aromatic compounds, halogenated substances, alkanes and oxygenated organics; the main odor contribution types included organic sulfides, aromatic compounds and oxygen-containing organic matter; 7 areas near the soil and air all had carcinogenic risks (>1.0×10-4), and 5 areas had non-carcinogenic risks. The main carcinogens were 1, 4-dichlorobenzene, benzene, and carbon tetrachloride.
CONCLUSIONS The results of the continuous study on the analysis of odor components and the risk of disease and cancer in pesticide sites provide an important basis for the restoration of the ecological environment and the health protection of residents in the study area.
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表 1 土壤采样深度
Table 1. Sampling depth
采样区域 采样深度 生产区 SC-1(0.4m)，SC-2(0.5m)，SC-3(1.2m)，SC-4(1.4m)，SC-5(2m)，SC-6(2.3m) 磷合成区 LHC(2m) 中间体生产区 ZJT-1(0.5m)，SC-2(1.0m)，SC-3(1.5m) 危险品储存区 CC-1(0.5m)，CC-2(1.0m)，CC-3(1.1m)，CC-4(1.3m)，CC-5(1.8m)，CC-6(2.5m) 包装仓库区 CK-1(0.6m)，CK-2(0.8m)，CK-3(1.7m) 办公区 BG(2.0m) 污水处理区 WS-1(0.5m)，WS-2(1.0m) 
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表 2 各点位臭气浓度和现场气味描述
Table 2. Description of odor concentration and odor for sites
点位名称 臭气浓度 现场气味描述 点位名称 臭气浓度 现场气味描述 SC-1 5495 微弱农药味 CC-2 17378 微弱农药味 SC-2 72443 农药味 CC-3 3090 微弱农药味 SC-3 13182 强烈农药味 CC-4 72443 微弱农药味 SC-4 30902 强烈农药味 CC-5 309 有机溶剂气味 SC-5 54945 强烈农药味 CC-6 13182 柚子皮味 SC-6 22908 强烈农药味 CK-1 17378 刺激性气味 LHC-7 9772 微弱农药味 CK-2 309 有机溶剂气味 ZJT-1 1318 有机溶剂气味 CK-3 416 有机溶剂气味 ZJT-2 1318 有机溶剂气味 BG 9772 微弱农药味 ZJT-3 416 柚子皮味 WS-1 549 强烈刺激性气味 CC-1 41686 微弱农药味 WS-2 3090 刺激性臭味
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表 3 臭味化合物的毒理学特性
Table 3. Toxicology of the odorous compounds
化合物 RfC [mg/(kg·d)] SF (kg·d/mg) 化合物 RfC [mg/(kg·d)] SF (kg·d/mg) 苯 0.03 0.015 四氯化碳 0.1 0.07 甲苯 5 - 六氯乙烷 0.03 0.04 间-二甲苯 0.1 - 1, 3-丁二烯 0.002 0.29 对-二甲苯 0.1 - 六氯丁二烯 - 0.078 邻-二甲苯 0.1 - 溴苯 0.06 - 1, 2, 3-三甲苯 0.06 - 苄基氯 - 0.17 1, 2, 4-三甲苯 0.06 - 1, 4-二氯苯 - 0.8 1, 3, 5-三甲苯 0.06 - 硫化氢 0.003 - 氯甲烷 0.6 0.002 二硫化碳 0.7 - 1, 1-二氯乙烯 0.2 - 甲硫醇 0.7 - 1, 2-二氯乙烷 - 0.091 乙醛 0.009 - 1, 2-二氯丙烷 - 0.004 四氢呋喃 2 - 二氯一溴甲烷 - 0.062 甲基异丁酮 3 - 三氯乙烯 0.003 0.046 乙腈 0.06 - 四氯乙烯 0.04 0.0021 正己烷 0.7 - 注：“-”表示没有相关记录。
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